Method of preparing catalytic material



Patented June 27, 1933 UNITED STATES MURRAY R ANEY, F CHATTANOOGA, TENNESSEE METH OD OE PREPARING CATALYTIC MATERIAL No Drawing.

My present invention relates to a method of preparing catalytic material such as may be used in the hydrogenation of oils, fats, waxes, and other hydrogenations and other catalytic reactions.

An object of the invention is to produce a catalytic material by the combination in an alloy of'various proportions of a catalytic material and other material or materials,- and also to produce materials having maximum catalytic properties by "a novel method of treatment of such an alloy.

To this end the invention contemplates forming the alloy of a catalytic material and other material or materials, and treating the alloy with a gas such 'as hydrogen under suitable conditions of temperature and pressure and moisture in the gas, or moistening the powdered alloy after the gas treatment is highly catalytic.

The invention also contemplates treating the alloy with sodium hydroxide or other solvent. which is a solvent of one or some only of the materials forming the alloy, in an amount insuflicient to completely dissolve that material, the resulting product, after finishing substantially free from alkali,-having catalytic properties.

The catalytic properties of this material may be further enhanced'hy treatment with hydrogen gas, under suitable conditions of temperature and pressure.

The invention further contemplates treat' ing the alloy in cold water, or hot Water, in water at the boiling point at atmospheric Application filed December 31, 1930. Serial No. 505,957.

pressure, or in hot water or steam under pressure. The invention also contemplates in general, the treatment of the alloy with water which has had its boiling-point raised by the addition of sugar, salt, and various other Water soluble salts or compounds, that would in effect raise the boiling point of the water and thereby subject the alloy to ahigher temperature Without or independently of the application of pressure.

The catalytic properties of the material resulting from the aqueous treatment may be enhanced by treatment with hydrogen gas under suitable conditions of temperature and pressure.

I preferably use nickel as the primary or catalytic material of the alloy, although the: invention contemplates also iron, copper, cobaltv and other catalytic materials. As the secondary or other material of the alloy, which material may be non-catalytic, I prefrably use aluminum or silicon although other materials may be used.

In carrying out the invention with nickel as the catalytic material and aluminum as the other material or one of the other ma terials, as there may be others, the .nickel and aluminum with or without other materials, are alloyed together by melting, either separately or together, and combining in a suitable vessel in proportions ranging from 1 to of nickel and from to 15% of aluminum. i

After the melt has fused and been thor- 85 in any desired apparatus to the action of 90 hydrogen gas under suitable conditions of temperature and pressure, preferably above atmospheric pressure and normal temperature. I have found approximately twenty pounds per square inch and 300 F. to be very desirable conditions. The How of hydrogen gas is preferably maintained for a considerable time, approximatel four hours giving good results, and prefera ly moisture should be present and may be provided in uct havin strong catalytic properties.

I have a so found that when the nickel aluminum alloy, as above produced, is sub ected to the action of a solution of sodium carbonate preferably at a boiling temperature, the sodium carbonate solution being at any concentration up to saturation, a catalytic material is produced. I am not aware of the exact chemical reaction which takes place at this point, but the resultant product is ex-. tremely voluminous, due probably to the reaction between the alkali and the aluminum,

although the nickel may possibly enter into the reaction. This solid product, to wit, the result of the reaction between the alkali solution and the alloy, and after washing substantially free from alkali and with or without separation from other by-products and impur1ties,'is catalytic and may be used in the hydrogenation of oils or other hydrogenations or other catalytic reactions.

Myex eriments with different strengths of alkali in the solution used for digesting the nickel aluminum alloy lead to the dlscovery that the aluminum is changed into an insoluble compound of aluminum such as aluminum hydrate Al O (3H O) and is left with the nickel or other catalytic material to form a voluminous catalytic substance. It Ina be that the sodium carbonate raises the boi ingflpoint of the solution which makes more e ective the reaction between the aluminum and the water in the solution to produce the aluminum hydrate a follows 2Al+6H 0=Al 0 311 0 3H,

Whether the sodium carbonate reacts with the aluminum or not, the resultant voluminous material contains an insoluble material in addition to the nickel and is actively catalytic.

This catalytic product may be separated or not from other products or materials, and subjected, either in the wet or dry stateyto the action of hydrogen gas under approximately similar conditions of temperature and pressure for approximately the same period of'timc as suggested above. The resultant end product is of an active catalytic and V0- luminous nature.

A vo uminous catalytic material may also a be produced by replacing the sodium carbonate in the above instances by a solution of sodium hydroxide or other solvent of the aluminum, insufficient in amount to completely dissolve the aluminum of the alloy, the resultant product, after washing substantially free from alkali, being of voluminous nature and having catalytic properties.

This voluminous catalytic product resultin from the treatment with the amount of so vent insuflicient to dissolve all of the aluminum, may be further treated for enhancement of catalytic properties b the h drogen gas treatment under suitab e con itions of pressure and temperature.

Reference is made to the treatments with caustic soda to dissolve substantially all of the aluminium or other non-catalytic material to leave the catalyticmaterial 1n finely divided condition as set forth in my Patents 1,563,587 of Dec. 1, 1925 and 1,628,190 of May 10,1927.

According to the present invention an amount of caustic soda insufficient to dissolve all of the aluminum is used. One example of the treatment of the present invention would be to use enough caustic soda to dissolve all but say 5% to of the aluminum which would remain in the catalytic material as metallic aluminumprobably mixed with aluminum hydrate. Another example would be to use caustic soda in such quantity that to of the aluminum remains undissolved. In this example the aluminum would be left largely as aluminum hydrate. In both cases a voluminous catalytic material is obtained.

' The equation showing the reaction of aluminum with caustic soda may be' shown as follows:

2A1 2NaOH 2H,() Al Na O 3H 54 8O 36 164 6 From this equation the theoretical weight of caustic soda required to convert aluminum into sodium aluminate is 1.48 times the weight of the aluminum, or for every pound of aluminum there is required 1.48 pounds of caustic soda. If only 90% of the aluminum was to be converted into sodium aluminate we would use 1.33 pounds of caustic per pound of aluminum. If we were to use .74 pound of caustic per pound of aluminum theoretically one half of the aluminum would be converted into sodium aluminate. But the unconverted part would be changed into aluminum hydrate by the water. In actual practice caustic soda inexcess of the theoretical amounts would be used to obtain the results illustrated.v

I have discovered that I can obtain a voluminous catalytic material similar to that produced by the treatment of the nickel aluminum alloy with sodium carbonate and" the treatment with insuflicient sodium hydroxide or caustic soda, by using unheated water alone, or heated water at atmospheric pres-- sure or greater, or steam under pressure or at atmospheric pressure, and in general with water which has had its boiling point raised by the addition of sugar, salt and various other water soluble compounds.

Treatment with cold or unheated water, that is water at normal temperature of say about Fahrenheit is effective but requires {a longer time than water at say 180 F ahrenheit.

In preparing the catalyzer with water the nickel aluminum powder may be boiled in water at atmospheric pressure. This treat-- ment is rather slow and may require a number of hours. In the treatment with water the finely divided aluminum apparently reduces the water, liberating the hydrogen in the water and uniting with the oxygen to form aluminum hydrate which reaction may be shown as follows:

'tion. For working at atmospheric pressure the boiling point of the water may be raised by adding various water soluble compounds such as sugar, ordinary salt, and calcium chloride, but I find that although the addition of these materials will raise'the boiling point of the water the reaction with the aluminum powder is not as materially accelerated as with the use of sodium bicarbonate added to the water.

A very much more effective and convenient way for raising the, boiling point is to digest the nickel aluminum powder in a closed vessel with water or steam under pressure. This is accomplished simply by putting the powder and water in a suitable vessel and'introducing steam directly into the vessel or heating the contents in any other convenient way. During the digesting operation the tank is vented enough to discharge the hydrogen which is generated.

It is to be noted that in the foregoing discussion covering the treatment that converts the aluminum into aluminum hydrate I have shown that this compound carries three molecules of water; For some purposes it is desirable that most of this Water of crystallization be removed and it is sometimes necessary to heat the catalyzer containing the aluminum hydrate under hydrogen gas at a temperature which may 'run as high as 7 00 F. All of the water would not be drivon off at this point and when any operation 50 required that substantially all of this water V be driven oh? the catalyzer material containing aluminum hydrate might have to be heated in air to a temperature as high as 1500 F.

After being exposed to air at this temperature substantially all of the water would be driven off but at the same time other changes would take place and the material would no longer be catalytic without subsequent treatment as follows.

The material which had been heated up to 1,500 F. in the air would then be placed in a suitable vessel and treated with hydrogen at a temperature between 500 and 600 F. until the escaping gas would not show the presence of any moisture. The moisture in The hotter the water the quicker the ac-' the escapin gas in this stage would be formed by t e reducing action of the hydrogen 'on any r'educeable oxides that were formed during the heating operation in air. I do not desire to be limited to the temperatures given as conditions may require less or greater temperatures to drive off the water from the aluminum hydrate. Also I do not want to claim that the aluminum hydrate is in any sense an inactive material. In other words, it is not intended to be simply a/support or carrier for the nickel but according to my best judgment and belief does contribute to the catalytic value.

I do not desire to limit the invention to aluminum as the non-catalytic material or other material, nor to nickel as the catalytic material, nor to the solvents mentioned, as other materials may be used within the scope of the invention.

The material need not necessarily be pulverized to a fine powder but it is ood practice to prepare a given weight 0% the catalytic material in a form having as large a surface as possible particularly'when the catalytic material is to be used in a liquid medium. For use with gases it is necessary to have the catalytic material in pieces largeenough to keep them from being carried out of the reacting chamber by the gases. To accomplish this result with precipitated catalyzers which are usually in a finely divided state, it is necessary to bind the catalyzer with some porous type of cement.

In addition to use in hydrogenation of oils, fats, and waxes, the catalytic material, produced according to my methods above set forth, may be used in other hydrogenations such as gaseous hydrocarbons, and nitrogen.

The chemical ,equations that I have given are meant to show comparative results. I do not know that these equations might not be subject to criticism by more experienced chemists and might not be considerably modified. However, they serve the purpose for which they are intended and even though the equations might be changed the relative reactions would still hold true.

I claim: 1

1. Aprocess of preparing catalytic material which consists in forming an 'alloy of a catalytic material with another material, and treating the alloy with hydrogen gas under elevated temperature and pressure, and in the presence of moisture.

2. A process of preparing catalytic material which consists in forming an alloy of catalytic material with another material, reducing the alloy to a powder and treating the powdered alloy with hydrogen gas under 125 elevated temperature and pressure and in the presence of moisture.

3. A process of preparing catalytic material which consists in forming an alloy of a catalytic material with another material, re-

ducing the alloy to a powder, treating the powdered alloy with hydrogen gas at. a temperature of approximately 300 F. and a, pressure of a proximatel twenty pounds per square inc and quenc g the resultant product in water.

4. A process of preparing catalytic material which consists in-allolying nickel with aluminum, reducing the a loy to a powder and treating the nlckel aluminum powder with hydrogen gas under elevated temperature and pressure and in the" presence of moisture. 5

5. A process of preparing catalytic mate rial which consists in formin an alloy of a catalytic material with anot er material,

and treating the alloy with sodium carbonate solution. 4

6. A recess of preparing catalytic material which consists in forming an alloy of a catalytic material with another material,

pulverizing the alloy, and treating the pow,-

. carbonate solution.

9. A process of preparing catalytic material which consists in alloying nickel with aluminum, pulverizing the alloy, treating the powdered alloy with sodium carbonate solution,'and washing the resultant product substantially free from alkali.

10. A method of preparing catalytic material which consists in alloying nickel and alu: minum, treating the resultant alloy withsodium carbonate in solution, and then separating the solid material from the supernatant liquid.

11. A process of preparing catalytic material which consists in forming an alloy of a catalytic material. with another material, treating the alloy with sodium carbonate solution, and treating the resultant solid material with hydrogen gas.

12. A process of preparing catalytic material which consists in forming an alloy oi catalytic material with another material, reducing the alloy to a powder, treating the powdered alloy with sodium carbonate solution, washing substantially free from alkali, and treating the resultant solid material with hydrogen gas." I

13. A process of preparing catalytic material, which consists in alloying nickel and ..aluminum, treating the resultant alloy with a solution of sodium carbonate, and thensubjecting the solid material so produced to the action of hydrogen gas. 14. A process'of preparing catalytic material, which consists in alloying nickel and aluminum, treating the resu tant alloy with a solution of sodium carbonate, and then subjecting the solid material so produced to the action of hydrogen gas under heat and pressure. 4

15. A process of pre aring catalytic material, which consists in a loying nickel and alu minum, treating the resultant alloy with a solution of sodium carbonate, and then sub- Jjecting the solid material so produced to the action of hydrogen gas while wet.

rial which consists in forming an alloy of a catalytic material with another material, and treating the alloy with a solvent only of said other material insufficient in amountto completely dissolve said other material. I

17 A process of preparing catalytic material which consists in forming an alloy of a catalytic material with other material, reducing the alloy to a powder, and treating the powdered alloy with a solvent only of said other material insuflioient in amount to completely dissolve said other material.

16. A process of preparing catalytic mate 18. A process of preparing catalytic material which consists in alloying nickel with aluminum, reducing the alloy to a powder and treating the powdered alloy with a solvent only of' the aluminum insufficient in amount to completely dissolve said aluminum.

19. The process of preparing catalytic material which consists in alloying nickel with aluminum, reducing the alloy to a powder, and treating the powdered alloy with sodium hydroxide solution insufficient in amount to completely dissolve said aluminum.

20. The process according to claim 16 including the steps of washing substantially free from alkali and treating with hydrogen gas under elevated temperature and pressure and in the presence of moisture.

21. A process according to claim 19 in which the amount of sodium hydroxide is such as to leave approximately five to ten per cent of the aluminum undissolved.

22. A process according to claim 19 in which the amount of sodium hydroxide is such as to leave approximately forty to fifty per cent of the aluminum undissolved.

23. A process of preparing catalytic material which consists in forming an alloy of a catalytic material with another material, pulverizing the alloy, treating the powdered alloy with heated water or steam withpressure to produce a catalyzer, and heating the catalyzer under hydrogen to a temperature such as to' driveoif some of the water and to enhance the activity of said catalyzer.

24. A process of preparing catalytic material which consists in alloying nickel with aluminum, reducing the alloy to powder, boiling the powdered alloy in water to produce a voluminous catalyzer.

25. The process of claim 24 in which the I boiling of the powdered alloy in water is carried on under pressure.

26. The process of claim 24 in which the water contains a material in solution to raise the boiling point, said material being inactive with respect to the nickel.

27. A process of preparing catalytic material which consists in allo g nickel with aluminum, reducing the a loy to powder,

treating the powdered alloy with heated water or steam under pressure to produce a voluminous catalyzer, heating the catalyzer under hydrogen to a temperature such as to drive ofi some of the water of crystallization associated with the aluminum, heating the catalyzer in air to a higher temperature-required to drive ofi substantially all of the water, and then heating under hydrogen again.

'28. A prc cess of preparing catalytic material which consists in alloying nickel with aluminum, reducing the alloy to powder, treating the powdered alloy with heated water,.or steam under pressure to produce a voluminous catalyzer,heating the catalyzer in air to a high temperature required to drive off substantially all of the water, and then heating under hydrogen.

29. The process of preparing catalytic material which consists in formin an alloy of a catalytic material with another material, reducing the alloy to powder, and boiling the powdered alloy in water to produce a catalyzer.

30. The process of claim 29 in which the water contains a substance in solution to raise the boiling point, said substance being inactive with respect to the nickel.

31. 'A' process of preparing catalytic material which consists in forming an alloy of a catalytic material and another material,

A and partially dissolving said other material with a non-acidic solvent therefor, said solvent being inactive with respect to the catalytic material, leaving the catalytic material in a finely divided state. 32. A process of preparing catalytic material which consists in forming an alloy of a catalytic material and another'material,

and partially 'separatingsaid other ,material from the catalytic material with a solution of a non-acidic substance chemically reactive with the said other material and inactive with res ect to the catalytic material.

testimony whereof,

- MURRAY my,

I afiix my signature. 

